Printed electric circuits



June 7-1960 w. G. LEE

PRINTED ELECTRIC cIRcuITs Original Filed April 1l, 1955 F/G. I

LZNQA W5 @l cfu M E H m H6 Mm 0f wm Z fu M Au 9 Q m m 7 M m INVENTOR. Warren G. Le@

BY im Unid Se@ Patent VC 2,940,018 PRINTED ELECTRlC CIRCUITS Warren G. Lee, AEast Chicago,v Ind., assigner to General American Transportation Corporation, Chicago, Ill., :incorporation of New York` original yapplication Apr. 11, l195s, serNo. 500,641.

Divided and this application Apr. 10, 195.7, Ser. No. 651,985

9 Clalmsf (Cl. `317-7401) The present invention-relates toV printedxelectric circuits. This applicationis a division of the copending application of Warren GQLee, Serial No. 500,641, filed April 1.1, 1955, and now abandoned.

- In accordance with a conventional method of making" a printed electric circuit, an adhesive layer (a resin-rubber base type layer) is applied to a previously sheared and punched insulating board (a laminate comprising a textile reinforced thennoset resin consisting essentially of vphenolformaldehyde condensation products), and thereover a thin coating of metallic silver is laid down (employing a ysilk screen step for pattern-control) by applying an aqueous solution Aof a silver salt and ia reducing agent. Thereafterrhollow -rivets v or eyelets are `se` curedinto the holesA previously-punched in' the bcard inV order Ito provide terminals -for the circuit elements of the printed electric circuit.

f This conventional method of making printed electric circuits is subject to several ,serious drawbacks: j

` (b) The rivets or eyelets employed as electrical terminals do not always make good electrical contact with the circuit elements and also require an assembly operation; and

(c') The silver ions migrate through the adhesive layer A further object of the invention is to provide an im-A proved printed electric circuit that employs no silver or other expensive electric conducting materials.

' `A further object of the invention is to provide a. printed electric circuit comprising an insulating supporting base, a nickel-phosphorus a-lloy layer intimately bonded to the surface of the base and a copper layer intimately bonded to the alloy layer.

Further features of lthe invention pertain to the particular arrangement of the elements of the printed electric circuit,y whereby the above-outlined and additional operating features thereof are attained.

The invention, both-as to its organization and principle of operation, `together with further objects and advantages thereof, will best be understood by reference to the following specification taken in connection with the accompanying drawing, in which:

Figure 1 is a after it has been (a) Thesilver coatingdoes not always adhere properly;I

prin-ted electric circuit that is not.

plan view of a sheet of insulating boardv shearedjand a pairof holes have been` 2,940,018 Patented June 7,41960 pierced therethroughand comprising the supporting element of a'pr'in'ted electric circuit;

l Fig. -2 is a vertical sectional view of the board taken; in the direction of the arrows along the line 2--2 in.v

Fig. 3 is a plan view of the board of Fig. 1 after a layer of nickel-phosphorus `alloy has been chemically plated upon faces thereof surrounding the pair of holes therein to define a pair of electrical terminals in the respective holes therein;

VFig. 4 is a vertical sectional View of the board taken in thedirection ofthe arrows along the line 4--4`in` Fig. 3; r j Fig. 5 is a plan view of the board of Fig. 3 carrying an electrically insulating organic masking layer upon the upper surface of the alloy layer, the masking layer having openings thereindepicting the outlines of a resistor and a capacitor extending between the pair of terminals carried thereby;

Y =Fig. y6 is `a vertical sectional view of Ithe board taken in the direction of ythe arrows along the line 6 6 in Fig. 5;

Fig. 7 `is. a plan view of the board of Fig. 5 after a copper layer has been electroplated upon the surfaces of the alloy layer that are exposed through the openings in the masking layer and upon the exposed surfaces of the pair of terminals, whereby the resistor and the capacitor are electrically connected in parallel relation between the pair of terminals; l A

Fig. 8 is ai vertical sectional view of the board taken in the direction ofthe arrows along the line 8--8 in Fig. -7; z

Fig. 9 is .aplan view of the Iboard of Fig. 7 after the masking layer has Abeen'dissolved and removed therefrom;v Fig. 10 is a vertical sectional viewlof the board taken in the direction of the arrows along they line 10-10 in Fig. 9; n

Fig. 1-1'is a plan view of the board of Fig. 9 after the exposed portion of the alloy layer has been dissolved and removed therefrom, and consequently the finished printed electric circuit; vand Fig. 12 is a vertical sectional view of the finished printed electric circuit taken in the direction of the arrows along the line 12--12 in Fig. 11. v

In Figs. 2, 4, 6, 8, 1() and 12, the thickness of the board, the layers, etc., have been greatly exaggerated; and in Figs. 5, 7, 9 and 11, the thickness of the outlines of the resistor and the capacitor have been greatly exag gerated; these exaggerated dimensions being so employed for the purpose of better illustration.

Referring now to the drawing, the construction and arrangement of the printed electric circuit will best be understood from the following description of the method of 'marking the same; however, it is noted that the iinished printed electric circuit 20 is shown in Figs. 11 and l2 as comprising an insulating vboard 21 carrying on the front.A

closure, since the present invention is directed to the structure of the printed electric circuit and the method of making the same, as contrasted with t-he composition of the printed electric circuit as employed ultimately in an electrical device,

Ithe upper surface thereof and upon the sur-` such as a radio-set, a television-y set, an electric control panel, etc.

Turning now to the method of making the printed electric circuit 20 and referring to Figs. 1 and 2, rst there is provideda sheared and pierced insulating board 21 that may comprise a laminate in the form of a textiler ing, blasting,vbrushing, grinding, bufling, abrading, cher'rli"` cal etching, etc., -so as to remove the` outer skin thereofin order to eliminate vany polarization ofthe surfaces thereof; This step produces the req'uired surface-rough ening and removal of the outside resin film from the sur-faces mentioned of Ithe board 21.v Specifieally, vapor blasting of these sur-faces of the' board 21 may be employed; and thereafter the board 21 is rinsed in tap water for about minutes at about 60 C. Then the surfaces mentioned of the board 21 are subjected to a vapor degreasing step; and then cleaned, for instance in a mild alkaline solution that may contain some detergent and some sodium carbonate. Again, the board 21 is rinsed in tap water for about 5 minutes at about 60 VC.A .Then the surfaces mentioned of the board 21 are acidiied in an aqueous solution containing 20% sul-furie aeid for :a Ashort time interval of about 1 to 5 minutes.' Again the board 21 is rinsed `as before; land next, the surfaces mentioned of the board 21 are activated in an aqueous palladiumchloride solution containing about 1000 p.p`.m'. of Pd++ for `a time interval of about l5 to 20 minutes.-

'Ihis aqueous solution may contain palladium chlorideV in anvamount of about 1.66 gms/liter. The board 21 is then dried in an oven, or with infra-red radiation, at about 80 C.v for a short time interval. Next, the board 2 1 is immersed in a reducing solution, such, for example, as an aqueous solution containing about 0.15 m.p.l.l of sodium hypophosphite o'r lhypophosphorous acid, the 'im mersion time being about 2 minutes. The board 21Ais rinsed for l5 seconds and `tlien immersed in an aqueous nickelstrike bath at room 'temperature' (about 70 F.) for about .10-20 minutes. The rinsing of the board 21 preceding the immersion thereof in the aqueous nickel strike bath is very important as it prevents decomposition of the` nickel strike bath by the carrying over with the board 21 of adsorbed Pd++ ions,

sodium acetate o.

The of this nickel strike bath is adjusted the approximate range 5.5 to 6.0 prior to use of sulfuric acid or sodium hydroxide being employed, as required.A The plating rate ofl this nickel strike lbath is about 0.04rniL/hr- Next, the board 21 is rinsed in tap water, and is then pickled in sulfuric acid (10%) for about 330l seconds;

again, the board'Zl is rinsed as before.

' llrcn the board 21 is subjected to chemical nickel platnig'k iria chemical nickel plating bath at about 200 F.- 210" F. to obtain the desiredthickness of the nickel layer deposited thereon (4 minutes being generally sutiicient), this chemical nickelplating bath having a plating rate of about 0.9to 1.0 miL/hourL o V l y The most suitable chemical knic-kel plating bath corn-A damore.

' mate composition:

y Prior to` use, the pI-{of this bath should lbe Iadjusted inthe prises an aqueous solution and may have the approxi- VM.p.l. Nickel sulfate 0.09 Sodium hypophosphite 0.225 M-alic acid i- Q.; LJL 0.18 Sodium succinate ,---n 0.06

approximate rangelv 5.8 @6.0 employing sulfuric acidfor sodium h'ydfsxise, as required. o l

Another suitable chemical nickel plating bath cornprises an aqueous solution and may have the vapproxin mate composition:

Prior to use, the pH of this bat-h should be -adjusted in the approximate range 4.5 to 4.7 employing sulfuric acid or sodium hydroxide, as required.

While either of the two above-described chemical nickel plating baths are entirely satisfactory for the chemical nickel plating of the prepared lsurfacesl of 4the -board 21V the malic-succinate bath first described is pre` -ferred since the adhesion of the nickel deposit is con- A, siderably greater employing this bath.

The Iabove-described process vof chemical nickel rplatingupon the surface of a non-metallic body is covered by ILS. Patent Nros.w2,690,40l and 2,690,402, granted on September 28, l1954, respectively to Gregoire Gutzeit,

- William J. Crehan and Abraham Krieg, yand to William `J`. Crehan.

After the last-mentioned chemical nickel platingj'step, the board Y2.1 is vremoved vto ari oven and heattreated at a temperature ofk about 325 F. for a time interval `of about 30 minutes in order to effect thorough drying and degassing thereof. o

Atthistime, the previously prepared nickel 23 and v24that `have been chemically plated thereupon, the layer-23 being dispos'edupon the front surface of ther board `2,1 and the' layers 24 being respectively dis-A posed, upon the surfaces Aof the :board 21 surrounding the holes 22 therein,` the layers 23 andk 24 being integrall and intimately bonded to the prepared surfaces'mentioned of the b oard ,'21. In the foregoing description of the integral layers 23 and 24, reference has been madetoV these layers as being formed of nickel; whereas, in fact,

they comprise an alloy of nickel and phosphorus, the.

alloy containing about 5 to 11% phosphorus by Weight.

In other words, the chemical nickel plating process tiescribed above automatically and inherentlyresults in the` plating upon the prepared surfaces of the layers 23 and 24 that comprise the nickel-phosphorus alloy mentioned. Accordingly, hereinafter the layers '23 and will be .re-y

ferred to as alloy layers; it being understood that thev alloy referred to is the nickel-phosphorus alloymentioned.

Recapitulating, the surfaces mentioned of theboard `21.` are prepared by roughening and cleaning so as to render.

, them non-polarized; and thereafter upon immersionv of the board 21 in the aqueous palladium chloride solution minute quantities of palladium chloride adhere to the preparedY surfaces mentioned. Thereafter, when lthe board 21 is immersed in the aqueous chemical reducing solution these minute quantities of palladiumchloride arev reduced to metallic'palladium so as to provide dispersed minute metallic palladium particles secured to lthe freshY non-'polarized surfaces mentioned. Subsequently, upon immersion of the board 21 in to the aqueous .chemical nickel strike bath, a nickel strike takes place upon these particles; and Suu subsequently `upon immersion ofthe board 21 into the aqueous chemiealVK nickel plating' bath',

surfaces ofthe Y board 21 carry, as shown' in Figs. 3 Aand 4, the layers ofc an alloy plating takes place upon these plated particles, which serve as growth nuclei, so that the thin continuous integral alloy layers 23 and 24 are produced upon the fresh non-polarized surfaces mentioned of the board 21; which integrallayers 23 and 24 are intimately and tenaciously bonded to the surfaces mentioned.

Next, the front surface of the board 21 is prepared for subsequent electroplating; and more particularly an electrical insulating organic masking layer 25 is laid down upon the alloy layer 23, employing a conventional silk screen technique and utilizing a conventional silk screen organic masking material that is insoluble in water and aqueous acid solutions, but is soluble in organic solvents. For example, the usual silk screen masking enamel is insoluble in water and in aqueous acid solutions, but is readily soluble in methyl ethyl ketone. Specifically, the masking layer 25 is laid down through the silk screen so as to `define or depict upon the alloy layer 23 the outlines of the electrical circuit elements of the finished printed electric circuit. By way of illustration, the masking layer 25 depicts the outlines of the resistor R and the capacitor C connected in parallel relationship between the pair of electrical terminals T1 and T2, as shown in Figs. 5 and 6.

After the masking layer 25 has been laid down upon the alloy layer 23 employing the conventional silk screen technique noted, it is then suitably dried; and thereafter the exposed surfaces of the alloy layer 23 are suitably cleaned. Then the board 21 is transferred to conventional electroplating equipment, including a copper elec- Itrode, and subjected to electroplating operations, the board 21 being immersed in an appropriate copper electroplating bath. Specifically, the alloy layer 23 is first subjected to a reverse current for about 30 to 60 seconds, in order to activate the same, the alloy layer 23 constituting the anode and the copper electrode constituting the cathode. After this activation, the alloy layer 23 is subjected to forward current in a conventional manner,-

the alloy layer 23 constituting the cathode and the copper electrode constituting the anode.

While a standard cyanide electroplating bath may be employed, the electroplating bath set forth below is even more advantageous in View of the circumstance that it is productive of a copper layer that is very tenaciously bonded to the alloy layer, as more fully explained hereinafter, the electroplating bath mentioned comprising an aqueous solution and having the approximate composition:

Cu'.(SO4).5H2O gm./l 188 H2804 conc. (66 B.) cc./l 61.5 Thiourea gm./l.. 0.01 Black strap molasses gnn/l-- 0.8 Wetting agent p.p.m 25

In passing, it is noted that after preparation of the electroplating bath mentioned, it should be filtered in order to remove therefrom any sediment; and also it is mentioned that any suitable wetting agent, such as the sodium salt of a sulfonated alkyl substituted aryl cornpound may be employed.

In the electroplating step, a current density of about 20,70 amps./sq. ft. (0.7-2 v.) may be employed with constant agitation of the electroplating bath.

At this time, the board 21 carries, as shown in Figs. 7 and 8, the layer of copper 26 upon the exposed surfaces of the alloy layer 23 and the layers of copper 26 upon the exposed surfaces of the alloy layers 24, the copper layers 26 and 27 being integral with each other and intimately bonded to the respective alloy layers 23 and 24. Accordingly, the copper layer 26 defines the resistor R and the capacitor C, while the copper layers 27, together with the alloy layers 24, define the terminals Ill and T2.

Themasking layer 25 is then dissolved and removed from the alloy layer 23 employing a suitable organic solvent, such, for example, as methyl ethyl ketone.

At this time, the youtlines of the resistor R and the capacitor C stand out in relief upon the alloy layer 23, as shown in Figs. 9 and l0.

The exposed portions or surfaces of the alloy layer 23 are then dissolved and removed from the front surface of the board 21 employing a suitable mineral acid wash, such, for example, as 1:1 nitric acid or 1:1 aqua regia or 2 parts sulfuric, l part nitric and A part water.

Ultimately the board 21 may be sheared to any configuration that may be required in the utilization of the printed electric circuit, if a configuration of the board 21 is required other than the initial rectangular configuration thereof. y

At this time, the finished printed electric circuit is produced, as shown in Figs. 1l and 12, wherebyvit will be understood that the terminals T1 and T2v comprise the composite of the residual alloy layers 24 and the copper layers 26 and 27; while the circuit elements R and C comprise the composite of the residual alloy layer 23 and the copper layer 26. Moreover, the circuit elements R and C are connected in parallel relation between the terminals T1 and T2, while the terminals mentioned are securely anchored in place in the holes 22 formed in the insulating board 21.

In the finished printed electric circuit 20, the circuit elements R and C are firmly anchored upon the front surface of the insulating boardr 21 and are integrally united with the terminals T1 and T2 thereby to provide a printed electric circuit having predetermined and fixed electrical characteristics throughout its useful long operating life. Furthermore, it will be understood that any circuit elements that may be carried upon the yrear surface of the insulating board 21 are formed thereon simultaneously with the formation of the circuit elements R and C on the front surface of the insulating board 21, as described above, and that any interconnections required between the circuit elements respectively carried upon the front and rear surfaces of the insulating board 21 are accomplished through the terminals T1, T2, etc., whereby the interconnected circuit elements carried on the respective surfaces of the insulating board 21 are integrally united by the terminals T1, T2, etc.

In the foregoing example, the chemical nickel plating process was described as a step in the lmethod of making the printed electric circuit, and it is indeed ideally suited to this method, but it will be understood that this process is in no way peculiar to this method. More particularly, the chemical nickel plating process is of general utility in the nickel plating of a wide variety of non-metallic bodies formed of such materials as: natural and synthetic plastics, wood, quartz, glass, ceramics, etc. Moreover, since the nickel strike bath described is employed at room temperature, the synthetic plastic materials may be either of the thermosetting class (phenol-aldehyde resins, polyalcohol-phthalic resins, urea-formaldehyde resins, etc.) or of the thermoplastic class (vinyl polymers, styrol resins, cellulose derivatives, casein materials, superpolyamides, acrylate polymers, etc.).

Considering now more particularly the aqueous chemical nickel strike bath, it is noted that while the optimum composition thereof is that previously set forth, the preferred composition thereof is as follows:

(l) Nickel ions-an absolute concentration in the' approximate range: 0.07 to 0.10 mole per liter.

(2) Hypophosphite ions-a ratio between nickel ionsand hypophosphite ions in the approximate range: 0.45 to 0.55.

(3) Acetate ions-a ratio between nickel ions and acetat ions inthe approximate range: 1.45 to 1.55. 'f'

(4) Ammoniuml ions--an absolute concentration in the .approximate range: 0.015 to 0.030 mole per liter.

(5) Ortho-boric acid-an absolute concentration in the approximate range: 0.015 to` 0,030 Irnoletper liter.. .a

7 (6) pH--within the range 5.5 to 6.0, adjust with sodium bicarbonate or sulfuric acid, as required.

In preparing this nickel strike bath the utilization of nickel hypophosphite is very convenient as it automatically establishes a ratio between nickel ions and hypophosphite ions of 0.5, but other soluble nickel salts (nickel sulfate, nickel chloride, etc.) may be used in. conjunction with other soluble hypophosphites (sodium hypophosphite, calcium hypophosphite, potassium hypophosphite, etc.).

Similarly, the ammonium ions may be derived from a wide variety of soluble ammonium compounds (ammonium sulfate, ammoniumy chloride, ammonium hydroxide, etc.), as it will be appreciated that it is the ammonium radical of this ingredient that is useful as a weak alkali to neutralize the boric' acid, thus forming a buffer active in the proper pH region.

Likewise, the acetate ions may be derived from a wide variety vof soluble acetates (sodium acetate, calcium acetate, potassium acetate, acetic acid, etc.), as it will bey appreciated that not only is the acetate abuifer (preventing 'substantial reduction in pH as the nickel ion rcduction-hypophosphite ion oxidation mechanism proceeds) vin the aqueous bath, but the acetate ion is a mild exaltant (increasing. somewhat the plating or striking rate) in the aqueous bath.

While there are a few soluble ortho-borates, other than ortho-boric acid, that might be used in preparing. the strike bath, there is no. point to the use thereof, since the ortho-borate ions immediately hydrolyze in the aqueous solution: v

to produce exactly the same borate ions that result from the use of ortho-boric acid in the aqueous solution:

bath is reduced below room temperature, the plating orv striking rate falls off substantially, whereby the lower temperature limit is about 50 F. from a practical stand point. The relationship between temperatures and plating rates of the bath are aboutV as follows:

MiL/hr. 50 F. 0.03 70 F. 0.04 85 F. 0.05

While the pH of the chemical nickel strikebath may vary considerably, as far as operability is concerned, the stability thereof is impaired at high pH and the plating rate is impaired at low pH; whereby, yfrom the operating rangeof pH-5.0 to 12.0, it is recommended that only the narrow band. of pH-5.5 to 6.0 be used, and that` the speciiic pli-5.8 `be employed as a practical matter.

`ln the present process of plating upon nonmetallic bodies, the utilization o-f the chemical nickel strikebath, preceding the utilization of the chemical nickel plating bath, is very advantageous as there is virtually nonickel plating initiation time (time required for the nickel plating upon theV dispersed growth nuclei palladium particles to begin) involved in the use of the strike bath, and the adhesion ofthe nickel layer (the principal portion of which is deposited by the plating bath) upon the bodies is very much improved. Moreover, the nickel layer (really a nickel-phosphorus alloy layer) is ideally suited toy receive the subsequent copper layer, as the el'ectrodep'- ositionfof. the copper is great-ly simplified by the nickel o t c layer of good conductivity. Furthermore, the bond between the copper, deposited electrically, and the nickel,

deposited chemically, is remarkable, as there is absolutely no peeling, blistering, spalling, or separation of any kind,

in every test that has yet been devised for studying this bond.

In the manufacture of a printed electric circuit designed to carry exceedingly small electric currents, the method can be modified in an obvious manner by prolonging the chemical nickel plating step and by omitting the copper plating step. Of course, in the resulting printed electric circuit the circuit elements are integral, as previously explained, fbut formed entirely in this modification of the described nickel-phosphorus alloy.

While there has been described what isV at present considered to 4be the preferred embodiment of the invention, it will be understood that various modifications may be made therein, and it is intended to cover in the appended claims all such modifications as yfall within the true spirit and scope of the invention.

What is claimed is:

1. A printed electric circuit comprising an insulating base, and a composite electric circuit element carried by the surface of said base and including inner and outer electrically conducting metal layers disposed in metal-tometal contact with each other, said inner layer being directly and intimately adhered to the surface of said base and consisting essentially of a nickel-phosphorus alloy, said alloy containing by weight about 89% to 95 nickel and about 5% to 11% phosphorus, said outer layer being directly and intimately adhered to said inner layer and consisting essentially of copper.

2. The printed electric circuit set for-th in claim 1, wherein said base is formed of a textile reinforced thermoset resin consisting essentially of phenol-formaldehyde condensation products.

3'. A printed electric circuit comprising an insulating base having a hole therethrough, a composite hollow terminal carried by said base within said hole and including inner and outer electrically conducting metal layers disposed in metal-to-metal contact with each other, said inner layer being directly and intimately adhered to the wall of said base surrounding said hole and consisting essentially of a nickel-phosphorus alloy, said alloy containing by weight about 89% to 95 nickel and about 5% to 11% phosphorus, said outer layer being directly and intimately adhered to said inner layer and consisting essentially of copper, and an electrically conducting circuit element carried upon the `face of said base andelec-tric'ally connected' to said terminal'.

4. The printed electric circuit set forth in claim 3, wherein said base is formed of a textile reinforced thermoset resin consisting essentially of phenol-formaldehyde condensation products.

5. A printed electric circuit comprising an insulating board having a pair of spaced-apart holes therein, a pair of hollow terminals carried by said board respectively within said holes and intimately adhered to the respectively adjacent surfaces thereof, and a composite circuit element carried by the surface of said 'board and extending between said terminals, said circuit element including inner and outer electrically conducting metal layers disposed in metal-to-metal contact with each other, said` inner layer being directly and intimately adhered to the surface'of said board and said outer layer being directly and intimately adhered to the surface of said inner layer, said inner and outer layers vbeing formed of different electrically conducting metals, and said 'terminals and said inner layer being of integral construction and conf' sisting essentially of a` nickel-phosphorus alloy containing by weight about 89% to 95% nickel and about 5% to 11% Phosphorus.

6. A printed electric circuit comprising an insulating' boardrhaving a hole therethrough, a hollow terminal' carried by said board Within said hole and intimately ad- 9 hered to the adjacent surface thereof, and a pair of composite circuit elements respectively carried by the surfaces of said -board and respectively extending to the adjacent ends of said terminal, each of said circuit elements including inner and outer electrically conducting metal layers disposed in metal-to-metal contact with each other, said inner layers being directly and intimately adhered to the respectively adjacent surfaces of said board and said outer layers being directly and intimately adhered to the respectively adjacent surfaces of said inner layers, said inner and outer layers in each of said circuit elements being formed of different electrically conducting metals, and said terminal and said inner layer in each of said circuit elements being of integral construction and consisting essentially of a nickel-phosphorus alloy containing by weight about 89% to 95% nickel and about to 11% phosphorus.

7. A printed electric circuit comprising an insulating boand, and a composite electric circuit element carried by the surface of said tboard and including inner and outer electrically conducting metal layers disposed in metal-tometal contact with each other, said inner layer being directly and intimately adhered to the surface of said board and said outer layer being directly and intimately adhered to the surface of said inner layer, said inner and outer layers being formed of different electrically conducting metals, and said inner layer consisting essentially of a nickel-phosphorus alloy containing by weight about 89% to 95% nickel and about 5% to 11% phosphorus.

8. In an article of manufacture, a construction coniprising three superimposed layers including a non-metallic supporting lbase layer and a metallic intermediate layer and a metallic surface layer, said intermediate layer being directly and intimately adhered to the adjacent surface of said base layer and consisting essentially of a nickel-phosphorus alloy, said alloy containing by weight yabout 89% to 95 nickel and about 5% to 11% phosphorus, and said surface layer being directly and intimately adhered to the `adjacent surface of said intermediate layer and consisting essentially of copper, whereby said intermediate layer and said surface layer are in :metal-to-metal contact with each other.

9. The article of manufacture set forth in claim 8, wherein said base layer is formed essentially of a substance selected `from the class consisting of glass material, ceramic material `and plastic material.

References Cited in the file of this patent UNITED STATES PATENTS 2,474,988 Sargrove July 5, 1949 2,532,283 Brenner Dec. 5, 1950 2,662,957 Eisler Dec. 15, 1953 2,690,403 Gutzeit Sept. 28, 1954 2,758,074 Black Aug. 7, 1956 2,834,723 Robinson May 13, 1958 2,848,359 Talmey Aug. 19, 1958 

1. A PRINTED ELECTRIC CIRCUIT COMPRISING AN INSULATING BASE, AND A COMPOSITE ELECTRIC CIRCUIT ELEMENT CARRIED BY THE SURFACE OF SAID BASE AND INCLUDING INNER AND OUTER ELECTRICALLY CONDUCTING METAL LAYERS DISPOSED IN METAL-TOMETAL CONTACT WITH EACH OTHER, SAID INNER LAYER BEING DIRECTLY AND INTIMATELY ADHERED TO THE SURFACE OF SAID BASE AND CONSISTING ESSENTIALLY OF A NICKEL-PHOSPHORUS ALLOY, SAID ALLOY CONTAINING BY WEIGHT ABOUT 89% TO 95% NICKEL 